Cationic slurry seal emulsifiers

ABSTRACT

An cationic emulsifier obtained from the reaction products of an alkyl phenol, polyamine, and formaldehyde or of an alkyl phenol, fatty acid/polyamine condensate, and formaldehyde and the uses of the emulsifier in cationic bituminous emulsions and paving slurry seal mixtures are disclosed.

This is a division of application Ser. No. 07/334,464, filed Apr. 7,1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to quick set slurry seal emulsions. Moreparticularly, it relates to novel emulsifiers for solventless andsolvent containing, mixing grade, oil-in-water cationic bituminousemulsions, which emulsifiers are the reaction products of alkyl phenols,aldehydes and polyamines.

2. Description of Related Art

In paving operations, three main practices are employed to achievethorough mixing of bitumen and aggregate:

(1) Mixing of free flowing heated asphalt (asphalt cement) withpre-dried aggregate;

(2) Mixing pre-dried aggregate with asphalt diluted with a hydrocarbonsolvent (cutback asphalt, cutter stock) at ambient temperatures; and

(3) mixing aggregate with asphalt emulsions, e.g., oil

in-water emulsions, obtained by vigorous agitation of asphalt and waterin the presence of an emulsifying agent.

Because of increasing cost in energy and hydrocarbon solvents andbecause of environmental concerns, the use of emulsified asphalt isincreasing.

Conventionally, emulsion slurry seals are formulated from mineralaggregate, which is a fine stone aggregate and/or mineral filler and amixing-grade, quick-setting or slow-setting emulsion containingbituminous residue (usually asphalt) and water to attain slurryconsistency. Usually, densely-graded aggregates, such as granitescreenings, limestone screenings, dolomite screening and blast furnaceslag, are combined with bituminous emulsions to produce slurry sealcompositions.

When a slurry seal is used in paving and road maintenance, the mixtureof emulsified bituminous material and fine-grained aggregate is held insuitable suspension until applied to the road surface. The slurry sealemulsion is of an oil-in-water type.

Depending on the emulsifier used to achieve an emulsion, anionic orcationic emulsions are obtained. In anionic emulsions, asphalt dropletsare negatively charged; in cationic emulsions, the asphalt droplets bearpositive charges.

In a bituminous emulsion formulated using cationic emulsifiers thebituminous material is deposited from the emulsion on siliceous orgranitic aggregate surfaces due to the attraction of polar chargesbetween the positively charged bituminous droplets and negativelycharged aggregate surfaces.

Cationic emulsions have been obtained by employing a variety of nitrogencontaining organic compounds, such as fatty amines, fatty diamines,fatty triamines, fatty amidoamines, fatty imidazolines, and reactionproducts of all these compounds with ethylene oxide and fatty mono- anddiquaternary ammonium salts. The fatty radical of these compounds canhave a variety of chemical structures, and the building blocks for thepreparation of these amines can be obtained from a variety of sources,such as petroleum refinates, animal fats, vegetable and fish oils, andtall oil. Amidoamines suitable as emulsifiers are disclosed in U.S. Pat.No. 3,230,104 to Falkenberg and in U.S. Pat. No. 3,097,174 to Mertens.Combinations of fatty monoamines and triamines are disclosed in U.S.Pat. No. 3,738,852 to Doi; fatty diamines are disclosed in U.S. Pat. No.3,728,278 to Trameli and U.S. Pat. No. 3,581,101 to Gzemski; fattyquaternary and diquaternary salts and modifications thereof aredisclosed in U.S. Pat. No. 3,220,953 to Borgfeldt, U.S. Pat. No.3,867,162 to Elste, U.S. Pat. No. 3,764,359 to Dybalski, U.S. Pat. No.3,957,524 to Doughty and U.S. Pat. No. 3,466,247 to Ohtuka, and fattyimidazolines are taught in U.S. Pat. No. 3,445,258 to Ferm. The use oftallow quaternary ammonium salts and tallow diquaternary diammoniumsalts for making emulsions suitable for slurry seal in solventlessapplications is described in U.S. Pat. No. 3,764,359 to Dybalski.

The uses of acidified reaction products of certain polycarboxylic acids,anhydrides, sulfonated fatty acids and epoxidized glycerides withcertain polyamines as emulsifiers yielding asphalt emulsions which canbe mixed with fine grained aggregate to give workable aggregate/emulsionmixes are disclosed in U.S. Pat. No. 4,447,269 to Schreuders et al.,U.S. Pat. No. 4,450,011 to Schilling al., U.S. Pat. 4,547,224 toSchilling et al., U.S. Pat. No. 4,462,890 to Schilling et al., U.S. Pat.No. 4,464,286 to Schilling, U.S. Pat. No. 4,561,901 to Schilling, U.S.Pat. No. 4,597,799 to Schilling, and U.S. Pat. No. 4,676,927 toSchilling et al. The use of a quaternary amine obtained by reactingepicholorohydrin, trimethylamine and nonylphenol for solventless mixesis disclosed in U.S. Pat. No. 3,957,524 to Doughty.

Quick-setting bituminous emulsion compositions wherein amine andalkanolamine salts of alkylbenzenesulfonic acid are used as emulsifiersare disclosed in the U. S. Patent No. 4,657,595 to Russell.

The general object of this invention is to provide novel versatilecationic emulsifiers for solventless and solvent containing, rapidsetting, mixing grade, oil-in-water bituminous emulsions.

Another object is to provide a cationic bituminous emulsion for mixingwith aggregates whose coating characteristics and set time can bevaried.

SUMMARY OF THE INVENTION

It has been found that emulsifiers capable of producing cationic quickset slurries may be obtained by the reaction product of an alkylphenolsuch as octylphenol, nonylphenol or dodecylphenol with a polyamine suchas aminoethylpiperazine and with an aldehyde such as formaldehyde.Cationic emulsifiers may also be obtained by using a fatty amidoamine orimidazoline in place of the polyamine. By varying the ratios ofreactants, a series of products with various molecular weights andvarious ratios of hydrophobe/hydrophile can be obtained.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The cationic slurry seal emulsifier of this invention comprises thereaction product of an alkyl phenol, a polyamine and an aldehyde by theMannich reaction, whereby nitrogen functionality is introduced onto thephenyl ring at the unsubstituted position ortho or para to the phenolichydroxyl group: ##STR1##

Any alkyl phenol may be used in the practice of this invention, so longas it has at least one unsubstituted position ortho or para to thephenolic hydroxyl group. Preferably the alkyl group has 8-20 carbons,most preferably 8-12 carbons. Examples of suitable alkyl phenols includeoctylphenol, nonylphenol, and dodecylphenol.

Polyamines suitable to undergo the Mannich reaction with formaldehyde orother aldehydes, as well as polyaldehydes are imidazoline formingpolyethylene amines and polyamines characterized by at least oneethylene diamine functional group with at least three hydrogens attachedto the two nitrogens. Compounds of this group which are able to giveboth amidoamines and imidazolines are: ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine, and higher homologues; N-aminoethylpropane diamine,N,N-diaminoethyl propane diamine and the N-aminoethyl orN,N-diaminoethyl substituted butane diamines, pentane diamines andhexane diamines, as well as N-hydroxy ethyl ethylene diamine. Thesecompounds have the general formulae:

    H.sub.2 NCH.sub.2 CH.sub.2 NHR

    R=H--, CH.sub.3 --, C.sub.2 H.sub.5 --, C.sub.3 H.sub.7 --,

    --CH.sub.2 CH.sub.2 OH, --(CH.sub.2 CH.sub.2 NH).sub.x H

    x=1, 2, 3, 4,...10

or

    R'R"N(CH.sub.2).sub.y NHR'"

    R'=H--, CH.sub.3 --, C.sub.2 H.sub.5 --, C.sub.2 H.sub.7 --, NH.sub.2 CH.sub.2 CH.sub.2 --,

    R"=H--, CH.sub.3 --, C.sub.2 H.sub.5 --,

    R'"=H--, CH.sub.3 --, C.sub.2 H.sub.5 --, C.sub.3 H.sub.7 --, NH.sub.2 CH.sub.2 CH.sub.2 --,

    y=2, 3, 4. 5, 6.

Amines capable of forming amidoamines but not imidazolines are:1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane;1,6-diaminohexane; piperazine (1,4-diazocyclohexane); N-aminoethylpiperazine; N-hydroxyethyl piperazine; N-aminopropyl propane diamine;1,3-N-methyl-N-aminopropylpropane diamine; 1,3-N, N-dimethylpropanediamine; 1,3-N, N-diethylpropane diamine; 1,3-N, N-dimethylethylenediamine; N-aminohexyl hexane diamine-1,6.

Diamines whereby the amino groups are separated by polyethylene oxidechains or polypropylene oxide chains are also very suited for theMannich reaction.

These compounds have the general formulae: ##STR2##

The above described amines can be further modified by reaction withalkylating agents or cross-linking agents such as are described in U.S.Pat. No. 4,775,744 by P. Schilling et al. in connection with ligninmodification. Modified amines or amine mixtures with increased molecularweight or amines which have additional reactive functionalities such assulfonic acid, carboxyl, hydroxyl, nitrile, and quaternary-ammoniumgroups will be obtained. For the aminomethylation, however, it isnecessary that at least one hydrogen on any of the nitrogens of theparent polyamine be available for the condensation with formaldehyde.

The polyamine as used in the practice of this invention may be a mixtureof two or more of the compounds described above. An example of acommercially available polyamine is the polyamine sold by Union Carbideunder the designation of Amine HH. Amine HH is a blend of polyaminesconsisting mainly of aminoethylpiperazine and triethylene tetramine.

Suitable reactants for the Mannich reaction include the following:aldehydes such as formaldehyde (the preferred reagent), benzaldehyde, orother tertiary aldehydes; dialdehydes such as glutaraldehyde andglyoxal; or unsaturated aldehydes such as acrolein or croton aldehyde.

To produce the emulsifier of the present invention, the desired amountsof alkylphenol and polyamine are blended and the mixture is diluted withisopropanol to make a approximately 70% solution. To this blend, thedesired amount of a 37% formaldehyde solution is added slowly withstirring (the reaction is exothermic). The mixture is heated to 90° C.for 3 hours.

The relative amount of alkyl phenol and polyamine added depends on thehydrophobe/hydrophile ratio desired in the final product. An increasingnumber of nitrogen atoms increases the solubility in mineral acids suchas HCl and H₃ PO₃.

The use of a polyamine in the Mannich reaction allows for cross-linkingthe polyamine with the aldehyde and results in a series of products withvarious molecular weights and various ratios of hydrophobe/hydrophile.Examples for this type of reaction are the products obtained fromp-dodecylphenol, formaldehyde, and aminoethylpiperazine:

Low molecular weight products: ##STR3##

Further products may be obtained by using fatty amidoamines orimidazolines in combination with or in place of the polyamine in thecondensation reaction with an alkyl phenol. Suitable fatty amidoaminesor imidzaolines include the condensation products of polyamines withtall oil fatty acid, or with tall oil fatty acid modified by theaddition of acrylic acid, methacrylic acid, fumaric acid or maleicanhydride. Examples of suitable fatty acid/polyamine condensates arefound in U.S. Pat. No. 4,447,269 issued to Schreuders, et al., and U.S.Pat. No. 4,561,901 issued to Schilling, the disclosures of which areincorporated herein by reference.

Fatty acid/polyamine condensates are available commercially fromWestvaco Corporation and are sold under the trademarks Indulin® RK-1,Indulin® MQK, and Indulin® MQK-1M. In the preparation of the emulsifierwith a fatty acid/polyamine condensate, the fatty acid/polyaminecondensate is blended with an alkyl phenol and the mixture is dilutedwith isopropanol. A 37% solution of formaldehyde is added slowly withstirring (the reaction is exothermic) and the mixture is heated at 90°C. for 3 hours.

Condensation products of p-dodecylphenol with formaldehyde and fattyacid/aminoethylpiperazine condensates can be visualized as follows:##STR4##

In preparing the cationic bituminous emulsions of this invention, anaqueous acidic solution of the emulsifiers described below is intimatelymixed with bitumen under high shear in a colloid mill. The bitumencontent can range from 30% to about 80% by weight, preferably between60% and 70%. The dosage of the emulsifier can range from 0.1-10% byweight of the emulsion, preferably between 0.5-2% by weight of theemulsion. Water makes up the remainder to 100%. Dependent on theemulsifier, a slurry

grade cationic emulsion is obtained in a pH range of 1-7, with theoptimum performance at a pH of about 1.5-2.5.

The "bitumen" used in the emulsion may be derived from domestic orforeign crude oil; it also includes bitumen, natural asphalt, petroleumoil, oil residue of paving grade, plastic residue from coal tardistillation, petroleum pitch, and asphalt cements diluted from solvents(cutback asphalts). Practically any viscosity or penetration gradedasphalt cement for use on pavement construction as described in ASTMdesignation D-3381 and D-946 may be emulsified with the aid of theemulsifiers of this invention.

In instances where it is desired to alter the performance of theemulsion to obtain improved viscosity at a given asphalt content orimproved stability to dust and fines, one of two methods may beemployed. Either a mixture of tall oil fatty acids, preferably tall oilpitch, can be added to the bitumen (asphalt) prior to emulsification tocontrol break time or improve the viscosity of the emulsion, or blendsof amidoamines with compatible cationic or nonionic emulsifiers may beused for the emulsification of the bitumen. Auxiliary emulsifiers, whichmay constitute up to 90% of the total combined emulsifier formulation,are fatty amines, fatty propane diamines, fatty amidoamines, and fattyimidazolines. Others are fatty monoquaternary ammonium salts and fattydiquaternary diammonium salts and nonionic emulsifiers, such as ethyleneglycol polyethers of nonyl- or dodecyl phenol.

A cationic soap solution is normally obtained by suspending the alkylphenol/polyamine/aldehyde reaction product or the alkyl phenol/fattyacid-polyamine condensate/aldehyde reaction product in water to which asufficient amount of a suitable acid, for instance hydrochloric,sulfuric, and phosphoric acid or the like is added until the desired pHvalue below 7 is reached and a clear emulsifier solution is obtained.Thereafter, the soap solution, which is preheated to 55° C., and thefluid asphalt, which is preheated to 120°-125° C., are mixed under highshear in a colloid mill to give asphalt emulsions of brown color andcreamy texture. Prior to testing according to ASTM D-244, the emulsionsare stored at 70° C. for 16 hours.

The paving slurry seal mixture is prepared by mixing a mineralaggregate, from about 8% to about 20% (based on weight of the aggregate)of the cationic bituminous emulsion, from about 4% to about 16% waterand up to 3% of an inorganic additive such as Portland cement, hydratedlime, limestone dust or fly ash, or an organic additive such as polymerlatex. Such additives should comply with the requirements of ASTM D-242.

The aggregates used in the paving slurry seal mixtures of this inventionare densely graded aggregates which range in size from anything passingthrough a No. 4 sieve to at least 80% retained on 200 mesh.

Depending on the type of aggregate and its cleanliness, mixing isimproved when aggregate is prewetted with 1-5% water by weight of theaggregate. The performance of the asphalt emulsions in regard to mixingcharacteristics and setting (higher percentage of one-hour washoff coat)can, if necessary, also be improved when, based on the weight ofasphalt, 1-15% of a solvent such a diesel oil is added to the asphaltprior to emulsification. The emulsions prepared with the emulsifiersdisclosed in this invention are stable and can be stored for a longperiod of time until required for use.

Depending on the intended application, the emulsion may be mixed withthe aggregate at a central mixing plant in a large pug mill and the mixtransported to the job site. Alternatively, the emulsion may be taken tothe job site and mixed there, either with a mixing device, such asmotorized mixing equipment, or manually.

As a paving technique at the roadsite, a mobile self-propelled unitcapable of uniformly metering the aggregate, water, inorganic andorganic additives emulsion components may be used. A typical unit isequipped with separate tanks for aggregate, water emulsion and additiveswhich are continually metered into a mixing chamber at a pre-determinedratio. The continually fed components are retained in the mixing chamberfor approximately one minute and then fed into a spreader-box andapplied to the surface to be coated. Batch operated pneumatic devicescan also be used for suitable placement of the bituminous aggregateslurries of this invention.

The practice of this invention may be seen in the following exampleswherein the preparation of various types of slurries of the invention isdescribed.

EXAMPLE 1

The following variety of alkyl phenol/polyamine/aldehyde emulsifierswere prepared for emulsion-aggregate slurry testing.

Emulsifier A

An emulsifier with a weight ratio of 52.8:37.5:9.2 of dodecyl phenol,Amine HH, and formaldehyde, respectively, was prepared as follows: 58.2gof dodecylphenol and 37.5g of Amine HH were dissolved inwater/isopropanol to yield a 70% solution. 24.86g of a 37% formaldehydesolution was added slowly with stirring and the mixture was heated threehours at 90° C.

Emulsifier B

An emulsifier with a weight ratio of 52.8:50:12 of dodecyl phenol, AmineHH and formaldehyde, respectively, was prepared as above.

Emulsifier C

Weight ratio of 52.8:50:12 of nonylphenol, Amine HH, formaldehyde,respectively, prepared as above.

Emulsifier D

Weight ratio of 52.8:75:18.1 of dodecylphenol, Amine HH, andformaldehyde, respectively, prepared as above.

Emulsifier E

Weight ratio of 52.8:87.5:21.1 of dodecylphenol, Amine HH andformaldehyde, respectively, prepared as above.

EXAMPLE 2

Cationic emulsions were prepared with 64% asphalt (either Exxon® 85/100penetration asphalt or Edgington hard base), 1.5% emulsifier at pH 2.5(adjusted with hydrochloric acid) and water to make up 100% (percentagesbased on weight of asphalt). Emulsions were prepared for each of theemulifiers described in Example 1.

Next, slurries were prepared by mixing, for each slurry prepared, 100grams of Camak (Georgia) granite screenings aggregate, 12 grams of acationic aqueous bituminous emulsion, and 14 grams water. Additionalsamples were prepared with 2 grams cement or 0.05 grams aluminum sulfateadded to the mix.

The materials were mixed in a mixing bowl until a homogeneous slurrymixture was obtained. This mix design is necessary to simulate fieldconditions. The inability to form a stable slurry within 1 to 2 minutesof mixing time when proper proportions of each ingredient are used wouldindicate a mixture in which the materials are not compatible. After theslurry was mixed, it was spread in a mold placed on an asphalt felt. Theset/break time was measured by blotting the exposed slurry surface witha paper towel. The slurry is considered to be "set" when no stain istransferred to the towel. Many other tests such as described in ASTMD-3910 could be used to measure strength and other physical propertiesof slurry. The Performance Guide for Slurry Seal published by theAsphalt Emulsion Manufacturers Association is used to measure theperformance of the slurry seal.

The percent of retained asphalt coating on the aggregate was determinedvisually after curing of the mixes at room temperature overnight andboiling in water for 10 minutes.

The slurry curing time was determined by means of a modified ASTM D-3910cohesive strength tester. The modified cohesive tester consistsessentially of (1) a frame, (2) instrument panel, (3) pressure gauge,(4) pressure regulator, (5) 4-way air valve and (6) a double-rod aircylinder mounted vertically so that a (7) rubber faced foot when loweredby air pressure against a specimen may be manually twisted to failure bya (8) peak-reading torque wrench.

Specimens are prepared and cast in a 60 mm diameter mold. A 6 mm-deepmold is used for aggregates 100% passing the 4.75 mm (#4 or 3/16" )sieve and a 10 mm-deep mold is used for aggregates 100% passing the 8 mm(5/16" ) sieve. The specimens are cast on 10 cm (4" ) squares ofnon-absorptive 16-pound bitumen mountings.

The modified cohesion tester is similar to the Armak ASTM D-3910-80machine except that it is designed for a constant regulated air supply,and has a convenient 4-way cylinder valve to operate the cylinder atcontrolled rate of speed. The cylinder is larger and more rugged. Thecontact foot used here is a flat 1/4" neoprene disc of 50-60 durometerhardness, 1-18" diameter rather than a 1" diameter plug cut from anautomobile tire. The procedures used may be found in ISSA TechnicalBulletin TB #139 12/82. The pressure exerted on the foot is 92.3% of thegauge reading. The test pressure is set at 200 kPa (28.44 psi) and thecylinder foot is lowered against the centered specimen and allowed tocompact the specimen for 5 to 6 seconds. The torque meter is placed onthe upper cylinder rod end and twisted by hand in a firm smoothhorizontal motion through 90° to 120° of arc within 0.7 to 1.0 second.The maximum torque pointer is read and the results recorded, the footraised and cleaned and torque pointer is reset.

A series of specimens were prepared by casting a fresh mixture into 6mmdiameter rings 6 or 10 mm thick and centered on a nonabsorbent surfacesuch as 10 cm squared of 15-pound saturating roofing felt. Peak torqueswere recorded at 5, 15, 30, and 60 minutes.

The flow behavior, set/break time and the percent of retained asphaltcoating on the aggregate was determined for slurries made withemulsifiers A, B, C, D, and E, with and without Portland cement oraluminum sulfate added to the mix. Cohesive strength testing was donefor slurries made with emulsifiers B and C with aluminum sulfate. Testsresults are set out in Table I below:

                                      TABLE I                                     __________________________________________________________________________    Evaluation of Nonylphenol and Dodecylphenol                                   Amine HH-Formaldehyde Condensates                                                         Mixing                  Cohesive Strength (psi)                   Type        Conditions.sup.a                                                                    Flow     Set %    after (min)                               Emulsifier                                                                          of Asphalt                                                                          (%)   Behavior (min)                                                                             Coating.sup.b                                                                      5  15 30 60                               __________________________________________________________________________    A     Edgington                                                                           --    Broke in 10 secs.                                                                      --  --                                                   Hard Base                                                                           2C    Broke in 05 secs.                                                                      --  --                                                         0.05Al                                                                              Excellent                                                                               60+                                                                              98                                             B     Exxon --    Broke in 30 secs.                                                                      --  --                                                   85/100 pen                                                                          2C    Broke in 05 secs.                                                                      --  --                                                         0.04Al                                                                              Excellent                                                                              60   95+ 8.6                                                                              10.5                                                                             13.4                                                                             HP.sup.c                         C     Exxon --    Broke in 20 secs.                                                                      --  --                                                   85/100 pen                                                                          2C    Broke in 05 secs.                                                                      --  --                                                         0.04Al                                                                              Excellent                                                                               60+                                                                               95+ 13.8                                                                             12.1                                                                             12.8                                                                             13.3                             D     Edgington                                                                           --    Good      1  90                                                   Hard Base                                                                           2C    Broke in 05 secs.                                                                          --                                                         0.05Al                                                                              Excellent                                                                              60  95                                             E     Edgington                                                                           --    Broke in 30 secs.                                                                      --  --                                                   Hard Base                                                                           2C    Broke in 05 secs.                                                                      --  --                                                         0.05Al                                                                              Excellent                                                                               60+                                                                              98                                             __________________________________________________________________________     .sup.a c: cement, Al: alum; % based on the weight of the aggregate.           .sup.b retained coating after boiling in water for 10 minutes.                .sup.c HP: hydroplaning  indicates strength in excess of 20 psi          

As seen from Table I, it was necessary to add aluminum sulfate retarderto the mixing water in order to achieve the desired mix stability. Whenno retarder was added, the break time became longer with increasingamounts of Amine HH and formaldehyde in the emulsifier molecule. Aftergoing through a maximum at a phenol:amine ratio of about 1:1.5 (bykeeping the Amine HH:formaldehyde ratio constant at about. 4.16:1) themix stability decreased again. Addition of 2% cement (Type III) causedpremature break of the mixes. Comparing condensates prepared fromdodecylphenol or nonylphenol with Amine HH and formaldehyde, emulsionsprepared with the latter broke faster when no retarder was added to themixing water. The cohesive strength development of the mix prepare withthe dodecylphenol derived polyamine containing emulsions was somewhatfaster. After 60 minutes, cohesive strength of at least 20 psi wasobtained as indicated by hydroplaning. Desirable adhesion results wereobtained with all the emulsions which could be properly mixed with theaggregate.

EXAMPLE 3

The following variety of fatty alkyl phenol/aldehyde/fattyacid-polyamine condensate emulsifiers were prepared foremulsion-aggregate slurry testing:

Emulsifier F

An emulsifier with a weight ratio of 80:10:0.74 of Indulin MQK,nonylphenol, and formaldehyde respectively was prepared as follows:

100g of Indulin MQK was blended with 12.5g nonylphenol and the mixturewas diluted with isopropanol. 2.5g of a 37% formaldehyde solution wasadded slowly with stirring and the mixture was heated to 90° C. forthree hours.

Emulsifier G

Weight ratio of 80:20:1.48 of Indulin MQK, nonylphenol and formaldehyde,respectively, prepared as above.

Emulsifier H

Weight ratio of 80:30:2.22 of Indulin MQK, nonylphenol and formaldehyde,respectively, prepared as above.

Emulsifier I

Weight ratio of 100:25:1.85 of Indulin MQK-1M, nonylphenol andformaldehyde, respectively, prepared as above.

Emulsifier J

Weight ratio of 100:50.3.7 of Indulin MQK-1M, nonylphenol andformaldehyde, respectively, prepared as above.

EXAMPLE 4

Cationic emulsions were prepared with 64% asphalt (Edgington hard base),1.5% emulsifier at pH 2.5 (adjusted with hydrochloric acid) and water tomake up 100% (percentages based on weight of asphalt). Emulsions wereprepared for each of the emulifiers described in Example 3.

Next, slurries were prepared by mixing Camak (Georgia) granitescreenings aggregate, a cationic aqueous bituminous emulsion, and waterin the same manner as described in Example 2.

The set/break time of each slurry and the percent of retained asphaltcoating on the aggregate were determined using the testing proceduresdescribed in Example 2. The results are reported in Table II, below:

                  TABLE II                                                        ______________________________________                                        Evaluation of INDULIN MQK and INDULIN MQK-1M                                  Reacted with Nonylphenol and Formaldehyde.sup.a                                     Mixing                                                                  Emul- Conditions.sup.b                                                                           Flow         Set   %                                       sifier                                                                              (%)          Behavior     (min) Coating.sup.c                           ______________________________________                                        F     --      14W 12E  Good        1     95+                                        2C      14W 12E  Excellent  20    80                                          0.05 Al 11W 12E  Excellent   60+   90+                                  G     --      14W 12E  Good        1    90                                          2C      14W 12E  Excellent   8    75                                          0.05 Al  9W 12E  Excellent   60+  95                                    H     --      14W 12E  Good        9     95+                                        2C      14W 12E  Poor        1    80                                          0.05 Al 10W 12E  Excellent   60+  95                                    I     --      14W 12E  Broke in 08 secs.                                                                        --    --                                          2C      14W 12E  Excellent   5    70                                          0.05 Al 10W 12E  Excellent   60+  95                                    J     --      14W 12E  Broke in 10 secs.                                                                        --    --                                          2C      14W 12E  Excellent   7    70                                          0.05 Al 10W 12E  Excellent   60+  95                                    ______________________________________                                          .sup.a Edgington Hard Base: 64% asphalt content; 1.5 emulsifier; pH          value: 2.5; Camakaggregate; Mixing time 30 secs.                              .sup.b W: water; E emulsion; C: cement; Al: alum; % based on the weight o     the aggregate.                                                                .sup.c Retained coating after boiling in water for 10 minutes.           

As shown above, the emulsifiers obtained from INDULIN MQK containing upto 37.5% nonylphenol (based on INDULIN MQK) could be mixed withaggregate with or without the addition of a set retarder. Excellentmixes were obtained in the presence of alum in the mixing water orcement in the aggregate as long as the nonylphenol content was nothigher than 25% based on INDULIN MQK.

Depending on the type of emulsifier and type and amount of retarder, settimes varied between one minute and one hour plus. Mixes containingcement showed less retained asphalt after subjection to the boilingtest.

Emulsions prepared with INDULIN MQK-1M/nonylphenol/ formaldehydecondensates could only be mixed with the addition of cement or alum tothe aggregates. Set times were less than ten minutes when 2% cementbased on the aggregate was used. In the presence of 0.05% alum, settimes were more than one hour.

While the invention has been described and illustrated herein byreferences to various specific materials, procedures and examples, it isunderstood that the invention is not restricted to the particularmaterials, combinations of materials, procedures and selected for thatpurpose. Numerous variations of such details can be employed, as will beappreciated by those skilled in the art.

I claim:
 1. A paving slurry seal mixture of an aqueous bituminousemulsion and mineral aggregate capable of being worked comprising: adensely graded mineral aggregate passing through No. 4 and at least 80%retained on 200 mesh screen; from about 8% to about 20% of an oil inwater type emulsion, based on the weight of the mineral aggregate,wherein the emulsion is comprised of from about 60% to about 70%bitumen, based on the weight of the emulsion, from about 0.5% to about2% of a cationic emulsifier based on the weight of the emulsion, andwater to make up 100% by weight of the emulsion; from about 4% to about16% water, based on the weight of the mineral aggregate, added to form aslurry of the aggregate and the emulsion; wherein the emulsifier is thereaction product of (a) an alkyl phenol of the form ##STR5## where Rrepresents a linear or branched alkyl group, (b) an aldehyde, and, (c)the reaction product of a polyamine and a compound selected from thegroup of a tall oil fatty acid, a polycarboxylic acid corresponding tothe formula ##STR6## and a polycarboxylic acid corresponding to theformula ##STR7## wherein x and y are integers from 3 to 9, x and ytogether equal 12, at least one Z is a carboxylic acid group and anyremaining Z is hydrogen.
 2. The paving slurry seal mixture of claim 1wherein said alkyl group comprises from 8 to 20 carbons.
 3. The pavingslurry seal mixture of claim 1 wherein said alkylphenol is selected fromthe group of octylphenol, nonylphenol and dodecylphenol.
 4. The pavingslurry seal mixture of claim 1 wherein said aldehyde is formaldehyde. 5.The paving slurry seal mixture of claim 1 wherein said polyamine is ablend of polyamines comprising aminoethylpiperazine and triethylenetetramine.
 6. The paving slurry seal mixture of claim 1 wherein saidalkyl phenol is selected from the group of octylphenol, nonylphenol anddodecylphenol, said aldehyde is formaldehyde, and said polyamine is ablend of polyamines comprising aminoethylpiperazine and triethylenetetramine.
 7. The paving slurry seal mixture of claim 6 wherein theemulsion is a rapid-setting, mixing grade composition.
 8. The pavingslurry seal mixture of claim 6 wherein said emulsion has a pH of from1.5 to 2.5.
 9. The paving slurry seal mixture of claim 8 wherein up to90% of the total emulsifier is comprised of one or more auxliaryemulsifiers selected from the group consisting of fatty amines, fattypropane diamines, fatty amidoamines, fatty imidazolines, fattymonoquaternary ammonium salts, fatty diquaternary diammonium salts, andethylene glycol polyethers of nonyl or dodecyl phenol.